Cyclogeraniolidenacetone and process of making same.



UNITED STATES Patented. August 23, 1904.

PATENT OF IC GEORG MERLING, OF FRANKFORT-ON-THE-MAIN, AND HEINRICH EIGH-VVEDE, OF HOOHST-ONTHE-l\IAIN, GERMANY, ASSIGNORS TO'FARB- WERKE, VORM.MEISTER, LUOIUS & BRIINING, OF HOOHST-ON-THE- MAIN, GERMANY, ACORPORATION OF GERMANY.

CYCLOGERANIOLIDE NACETONE AND PROCESS OF MAKING SAME.

SPECIFICATION forming part of Letters Patent No. 768,389, dated August23, 1904.

Application filed February 26, 1903.

To aZZ whom it mayboncern:

, Be it known that we, GEoRG MERLING, Ph. D., residing atFrankfort-on-the-Main, and HEINRICH EIoHwEDn, Ph. D., residing atHoohstonthe-Main, Germany, citizens of the Empire of Germany, haveinvented certain new and useful Improvements in the Manu facture ofAlpha and Beta Oyclogeraniolidenacetone, of which the following isaspecifica tlon.

We have found that by the action of sodium and carbonic acidontrimethylcyclohexanon trimethylcyclohexanoncarbonic acid having theformula 2 5 CH /CH may be obtained, which is transformed by reducingagents into trimethyl-oxy-cyclohexancarbonic ac1d,hav1ng the formula C von, on coon If the calcium salt of this acid is subjected to massbecomes crystalline toward the end of Serial Nu, 1%,250. (No specimens.)

dry distillation in a vacuum with the equimolecular proportion offormate of calcium, not

only the carboXyl of the acid is replaced by 59 the formyl, but alsowater is simultaneously eliminated in the nucleus. Thus cyclogeraniolenaldehyde is obtained and this in two isomeric modifications on, 0H

on, alpha-modification on, oH

beta-modification.

the operation. On the reaction beingcomplete ice-water is added, andtheaqueous solution is separated from the ethereal layer containingunchanged trimethylcyclohexanon. To eliminate the trimethylcyclohexanol,the aqueous solution after standing twentyfour hours is extracted withether and then acidified with dilute mineral acid, whereupon thetrimethylcyelohexanoncarbonic acid separates as acrystalline mass. Whenrecrystallized, it melts at 111 to 112 Centigrade, carbonic acid beingevolved.

Sec/202d. lllir/iufactmc of triinezfhy l 0 1 1 ()1/aye/0700:0021curb/mit: (la/Fl, Ctll1u (/0 ()H.- This acid is obtained bygradually introducing sodium amalgam, (about four thousand parts ofamalgam of two per cent. and a strong current of carbonic acid into thedilute, cold solution of trimethylcyclohexanoncarbonate of sodium, onehundred parts.) On the reaction being complete the oxy-acid isprecipitated as a crystalline mass on acidifying the solution separatedfrom the mercury. This acid crystallizes from ethly acetate in colorlessprisms, which melt at 185 centigrade and boil without decomposition at203 to 205 Centigrade, (ten millimeters) The sametrimethyl-oxy-cyclohexancarbonic acid, and one with thisstereoisomerical oXy-acid, is obtained by electrolytical reduction oftrimethyleyclohexanonearbonie acid.

Third. llflmufactm'c 0f01 070901man/501022alcZe/tydes, Ctlilifi. OOJZ-Athorough equimolecular mixture of the calcium salt oftrimethyl-oxy-cyclohexancarbonic acid and formate of calcium issubjected to dry distillation while passing over a weak current ofhydrogen under greatly-reduced pressure. At first water distils, thenthe aldehyde which collects as an oil in the receiver cooled with ice.hen purified with steam and subsequently subjected to fractionaldistillation, it is a colorless oil of agreeable odor, which melts at101 to 102 centigrade, (seventeen millimeters.)

Fourth. ilfil/wafaczfm'c 0f Q'I/C/Of/aHt/l(016(26- v'zacctom, ell/11:).(I'll I Off C][.-;.*To manufacture this compound with a satisfactoryyield offers certain difliculties, as the cyclogeraniolenaldehydeobtained by Example 3 consists of two isomeric modifications, (alpha andbeta,) of which the alpha condenses with acetone already at icetemperature, Whereas the beta condenses with acetone first at a hightemperature in presence of agents of alkaline reaction. Attempts tocondense a mixture of aldehyde With acetone at once at a hightemperature gave little satisfactory results, as the acetonecondensation products, especially that of the alpha-modification, arevery sensible toward agents of alkaline reaction, being furtherdecomposed and becoming resinous. e have found that these difficultiesmay be overcome by first condensing the more easily-reactingalpha-modification of temperature and in presence of very dilutealkaline agents or such of feeble reaction by isolating thebeta-modilication of the aldehyde not having entered into reaction amlby then causing acetone and condensing agents to act on it at a hightemperature. Any agent of alkaline reaction is suitable forcondensation, such as caustic potash, caustic soda, alkaline earths,magnesium, borax, sodium phosphate, sodium alcoholate, and the like.Condensation even occurs by heating the aldehyde with acetone alone in aclosed tube at a high temperature.

Example: Fifteen parts of cyclogeraniolenaldehyde (mixtures of the alphaand beta modifications having the point of ebullition 101 to 102centigrade, seventeen millimeters pressure) are dissolved in lifty partsof pure acetone, to which is added while cooling with ice a coldsolution of 0.75 parts of sodium in fifteen parts of absolute alcohol.The mixture is left standing in ice for one hour and at ordinarytemperature for some further hours, whereupon the solution becomesyellow-red and finally brown-red. It is then poured on ice, neutralizedwith tartaric acid, and the un changed aldehyde (beta-modilication) andacetone condensation product thus obtained are distilled with steam. Tenparts of the thus isolated betacyclogeraniolenaldehyde are dissolved inforty parts of pure anhydrmls acetone, and the solution is heated fortwentyfour hours, with one part of finely-ground barium oxid on theboiling-water bath. It is then filtered. The filtrate is diluted withwater, and the solution is saturated with carbonic acid. Thebeta-cyclogeraniolidenaeetone is driven over with steam and thenpurilied by distillation in vacuum.

CH: alpha-eye]ogeranhvlidenai-et me CH 3 (111,, y

Vhen concentrated they have an intense odor of cedar wood and whenstrongly diluted the aldehyde mixture with acetone at a low 1 that ofviolets.

Having now described our invention, What We clalm 1s 1. The processherein described of making.

a mixture of alpha and beta oyclogeranioliden- 5 acetone, which consistsin treating alpha and beta cyclogeraniolene aldehyde With acetone in thepresence of an alkaline agent, substantially as set forth.

2. As a new product, a mixture of alpha and I0 betacyclogeraniolidenacetone, being a colorless oil, boiling at 132 to 134centigrade (ten

